EP2855445B1 - Salt of bicyclic aromatic anions for li-ion batteries - Google Patents

Salt of bicyclic aromatic anions for li-ion batteries Download PDF

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EP2855445B1
EP2855445B1 EP13723888.7A EP13723888A EP2855445B1 EP 2855445 B1 EP2855445 B1 EP 2855445B1 EP 13723888 A EP13723888 A EP 13723888A EP 2855445 B1 EP2855445 B1 EP 2855445B1
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group
formula
salt
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EP2855445A1 (en
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Grégory Schmidt
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Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to bicyclic imidazole compounds, and their salts, their manufacturing processes and their uses, in particular as an electrolyte component for batteries.
  • a lithium ion or sodium ion battery comprises at least one negative electrode, a positive electrode, a separator and an electrolyte.
  • the electrolyte consists of a lithium or sodium salt dissolved in a solvent which is usually a mixture of organic carbonates, in order to have a good compromise between the viscosity and the dielectric constant.
  • lithium hexafluorophosphate LiPF 6
  • LiPF 6 lithium hexafluorophosphate
  • the prerequisites for having an electrolyte salt are a good chemical dissociation between the cation and the anion, which implies a negative charge on the anion delocalized or diminished by attracting effects.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • A represents a monovalent cation
  • X independently represents a carbon atom, an oxygen atom, a sulfur atom, a phosphorus atom or a nitrogen atom.
  • the substituents may be independently electron-withdrawing or electro-donor groups defined by a Hammett parameter (the Hammett parameter is a tabulated constant which is determined for a series of groups substituents by measuring the dissociation constant of the corresponding benzoic acids) between -0.7 and 1.0.
  • the substituents are chosen from a cyano group (CN), an R 1 group, an OR 1 type ether group, an N (R 1 ) 2 type amino group, and a CO 2 R 1 type ester group.
  • R 1 has the formula C n H m X ' p with n between 0 and 6, m between 0 and 13, X' is a halogen (F, Cl, Br and I) and p between 1 and 13.
  • the invention firstly relates to bicyclic imidazole compounds (IV) and their salts (V).
  • the invention relates secondly to the processes for producing bicyclic imidazole compounds (IV) and their salts (V).
  • the invention relates to the use of compounds of formula (V).
  • the salts of the bicyclic imidazole compounds (V) according to the present invention are represented by the above general formula wherein A represents a monovalent cation A, for example an alkali metal.
  • the preferred alkali metal is selected from lithium and sodium.
  • the salts (V) may be substituted.
  • the preferred substituents are electron-withdrawing or electro-donating groups, in particular those having a Hammett parameter between -0.7 and 1.
  • Particularly preferred electro-attracting and electro-donating groups are chosen from a cyano group (CN), a group R 1 , an ether group of type OR 1 , an amino group of type N (R 1 ) 2 , an ester group of type CO 2 R 1 , a sulfonyl group type SO 2 R 1 or a phosphonyl group type PO 2 R 1 .
  • R 1 has the formula C n H m X ' p with n between 0 and 6, m between 0 and 13, X' is a halogen (F, Cl, Br and I) and p is between 1 and 13.
  • the bicyclic imidazolates (V) can be prepared from the imidazole compounds (IV) by reacting it with an AZ base, with A having the same meaning as above and Z representing a hydride, hydroxide or carbonate anion.
  • AZ is selected from lithium hydride, lithium carbonate, lithium hydroxide, sodium hydride, sodium carbonate, sodium hydroxide and combinations thereof.
  • Compounds (IV) can be prepared from the condensation of an aromatic aldehyde of general formula (II) and DAMN (I).
  • the process for the preparation of the bicyclic imidazole compounds (IV) comprises (i) a reaction step of the DAMN of formula (I) with an aromatic aldehyde of general formula (II) at a temperature of between 0 and 80 ° C, preferably at 50 ° C, more preferably from 20 to 30 ° C, optionally in the presence of a solvent to give a compound of formula (III), followed (ii) a dehydrogenation step of the compound of formula (III).
  • Step (i) is preferably carried out in the presence of a solvent.
  • a solvent Any compound that solubilizes the reagent (s) can be used as a solvent.
  • the concentration of the DAMN in the reaction medium is preferably from 0.001 to 2 mol / l, more preferably from 0.1 mol / l to 1 mol / l.
  • the molar ratio of the compound (I) to the compound (II) is preferably from 0.25 to 1.5, more preferably from 0.5 to 1.25.
  • the duration of step (i) is preferably 1 to 12 hours, more preferably 1 to 5 hours, for example about 2 hours.
  • step (i) is carried out in the presence of an acidic catalyst, optionally by adding sulfuric acid or a carboxylic acid, such as trifluoroacetic acid, acetic acid or acid. benzoic acid in the reaction medium.
  • an acidic catalyst optionally by adding sulfuric acid or a carboxylic acid, such as trifluoroacetic acid, acetic acid or acid. benzoic acid in the reaction medium.
  • the temperature of the reaction can be constant throughout the first step.
  • the temperature is increasing throughout step (i).
  • Step (ii) can be carried out in the presence of a compound capable of reacting with hydrogen, such as oxygen, hydrogen peroxide and peroxides, N-chlorosuccinimide, N-bromosuccinimide, hydroxyl chloride, hydroxyl fluoride, quinone-type skeleton compounds
  • a compound capable of reacting with hydrogen such as oxygen, hydrogen peroxide and peroxides, N-chlorosuccinimide, N-bromosuccinimide, hydroxyl chloride, hydroxyl fluoride, quinone-type skeleton compounds
  • the bicyclic imidazole compound of formula (IV) is preferably isolated and purified.
  • the reaction medium can be evaporated and the imidazole (III) recrystallized from water and then recovered by filtration.
  • the solid obtained can be dissolved in an aqueous solution of AZ base, preferably lithiated or sodized with a concentration ranging from 10 -5 mol / l to the saturation concentration.
  • the compound salt of formula (IV) is formed the solution can undergo several treatments with activated carbon. The solution can then be evaporated to give the salt of formula (IV).
  • the compounds of formula (V) can be used for the preparation of an electrolyte, dissolving them in a suitable solvent.
  • the solvent may consist of at least one compound selected from carbonates, glymes, nitriles and sulfones.
  • carbonate there may be mentioned in particular ethylene carbonate, dimethylcarbonate, ethylmethylcarbonate, diethylcarbonate, propylene carbonate, glycerol carbonate.
  • ethylene glycol dimethyl ether diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether and diethylene glycol t-butyl methyl ether.
  • nitrites examples include acetonitrile, propionitrile, butyronitrile, methoxypropionitrile, isobutyronitrile and fluorinated compounds derived from the foregoing compounds.
  • sulfones examples include dimethylsulfone, sulfolane, ethylmethylsulfone, propylmethylsulfone, isopropylmethylsulfone, isopropylethylsulfone, tertbutylethylsulfone, tertbutylmethylsulfone and tertbutylpropylsulfone.
  • the solvent is preferably composed of a mixture of compounds, advantageously from 2 to 5, chosen from the carbonates and / or glymes and / or the sulphones mentioned above.
  • the proportions by weight of each of the compounds constituting the solvent are preferably between 1 and 10 with respect to the constituent in a smaller amount, more preferably between 1 and 8.
  • the concentration of compound of formula (V) in the electrolyte is preferably from 0.1 mol / l to 5 mol / l, more preferably from 0.2 mol / l to 2.5 mol / l.
  • the electrolyte consists of a mixture of at least two lithium salts selected from the imidazolate salt (IV), LiPF 6 , LiBF 4 , CF 3 COOLi, CF 3 SO 2 Li LiTFSI (lithium bis (trifluoromethanesulfonyl) imide), LiFSI (lithium bis (fluorosulfonyl) imide), lithium LiTDI (lithium 1-trifluoromethyl-4,5-dicarbonitrile-imidazolate) and LiPDI (1-pentafluoroethyl).
  • each lithium salt present in the mixture can vary within wide limits and generally represents between 0.1 and 99.9% by weight relative to the total weight of the salts present in the mixture, and preferably between 1 and and 99% by weight.
  • the solution is filtered and extracted with 2 times 250 ml of ether.
  • the aqueous phase is then treated with activated carbon for 2 hours at 50 ° C.
  • the solution is filtered and then evaporated.
  • the residue is then taken up in acetonitrile, the insoluble part corresponding to the lithium carbonate is removed by filtration.
  • the filtrate is then evaporated to give a yellow solid which is the lithium salt of the following formula:
  • the salt (V-1) is then dissolved at different concentrations in a mixture of ethylene carbon and dimethyl carbonate with a mass ratio of 1.
  • the ionic conductivity of the different concentrations is then measured by impedance spectroscopy (FIG. 1).
  • the electrochemical stability of the salt (V-1) relative to Li + / Li is then determined by cyclic voltammetry of a solution of salt (V-1) at 1 mol / L in an ethylene carbonate and dimethyl carbonate mixture with a mass ratio of 1 ( figure 2 ).

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Description

DOMAINE DE L'INVENTIONFIELD OF THE INVENTION

La présente invention concerne les composés imidazole bicycliques, et leurs sels, leurs procédés de fabrication ainsi que leurs utilisations, notamment comme composant d'électrolyte pour batteries.The present invention relates to bicyclic imidazole compounds, and their salts, their manufacturing processes and their uses, in particular as an electrolyte component for batteries.

ARRIERE-PLAN TECHNIQUETECHNICAL BACKGROUND

Une batterie lithium-ion ou sodium-ion comprend au moins une électrode négative, une électrode positive, un séparateur et un électrolyte. L'électrolyte est constitué d'un sel de lithium ou sodium dissous dans un solvant qui est généralement un mélange de carbonates organiques, afin d'avoir un bon compromis entre la viscosité et la constante diélectrique.A lithium ion or sodium ion battery comprises at least one negative electrode, a positive electrode, a separator and an electrolyte. The electrolyte consists of a lithium or sodium salt dissolved in a solvent which is usually a mixture of organic carbonates, in order to have a good compromise between the viscosity and the dielectric constant.

Parmi les sels les plus utilisés figure l'hexafluorophosphate de lithium (LiPF6), qui possède beaucoup des nombreuses qualités requises mais présente le désavantage de se dégrader sous forme de gaz d'acide fluorhydrique. Cela pose des problèmes de sécurité, notamment dans le contexte de l'utilisation prochaine des batteries lithium-ion pour les véhicules particuliers.Among the most used salts is lithium hexafluorophosphate (LiPF 6 ), which has many of the required qualities but has the disadvantage of degrading in the form of hydrofluoric acid gas. This poses safety problems, particularly in the context of the forthcoming use of lithium-ion batteries for private vehicles.

Les prérequis pour avoir un sel d'électrolyte sont une bonne dissociation chimique entre le cation et l'anion ce qui implique une charge négative sur l'anion délocalisée ou diminuée par des effets attracteurs.The prerequisites for having an electrolyte salt are a good chemical dissociation between the cation and the anion, which implies a negative charge on the anion delocalized or diminished by attracting effects.

Des sels basés sur l'effet attracteur ont donc été développés tels que le LiTFSI (bis(trifluoromethanesulfonyl)imidure de lithium) et le LiFSI (bis(fluorosulfonyl)imidure de lithium).Salts based on the attractor effect have therefore been developed such as LiTFSI (lithium bis (trifluoromethanesulfonyl) imide) and LiFSI (lithium bis (fluorosulfonyl) imide).

D'autres sels cette fois basés sur la délocalisation de la charge ont également été développés tels que le LiTDI (1-trifluorométhyl-4,5-dicarbonitrile-imidazolate de lithium), ainsi que cela est enseigné dans le document WO 2010/023413 . Mais ces derniers présentent des conductivités ioniques plus faibles que ceux précédemment cités.Other salts this time based on the delocalization of the filler have also been developed such as LiTDI (1-trifluoromethyl-4,5-dicarbonitrile-lithium imidazolate), as is taught in the document WO 2010/023413 . But these have lower ionic conductivities than those previously mentioned.

La demanderesse a découvert que la présence d'un second cycle aromatique permettrait d'augmenter la délocalisation de la charge négative et ainsi augmenter cette conductivité ionique.The applicant has discovered that the presence of a second aromatic ring would increase the delocalization of the negative charge and thus increase this ionic conductivity.

RESUME DE L'INVENTIONSUMMARY OF THE INVENTION

Dans ce qui suit, on désigne par

  • DAMN : le diaminomaléonitrile et est représenté par la formule (I)
    Figure imgb0001
  • Les composés (II) sont représentés par les formules générales développées ci-dessous. Ils sont désignés sous (IIa) lorsque le cycle aromatique est à 6 atomes et sous (IIb) pour un cycle aromatique à 5 atomes
    Figure imgb0002
  • Les composés (III) sont représentés par les formules générales développées ci-dessous. Ils sont désignés sous (IIIa) lorsque le cycle aromatique est à 6 atomes et sous (IIIb) pour un cycle aromatique à 5 atomes
    Figure imgb0003
  • Les composés imidazole bicycliques (IV) sont représentés par les formules générales développées ci-dessous. Ils sont désignés sous (IVa) lorsque le cycle aromatique est à 6 atomes et sous (IVb) pour un cycle aromatique à 5 atomes
    Figure imgb0004
  • Les sels des composés imidazole bicycliques (V) sont représentés par les formules générales développées ci-dessous. Ils sont désignés sous (Va) lorsque le cycle aromatique est à 6 atomes et sous (Vb) pour un cycle aromatique à 5 atomes
    Figure imgb0005
In the following, we designate
  • DAMN: diaminomalonitrile and is represented by formula (I)
    Figure imgb0001
  • The compounds (II) are represented by the general formulas developed below. They are designated under (IIa) when the aromatic ring is 6 atoms and under (IIb) for a 5 atomic aromatic ring
    Figure imgb0002
  • The compounds (III) are represented by the general formulas developed below. They are designated under (IIIa) when the aromatic ring is 6 atoms and under (IIIb) for a 5 atomic aromatic ring
    Figure imgb0003
  • The bicyclic imidazole compounds (IV) are represented by the general formulas developed below. They are designated under (IVa) when the aromatic ring is 6 atoms and under (IVb) for a 5 atomic aromatic ring
    Figure imgb0004
  • The salts of the bicyclic imidazole compounds (V) are represented by the general formulas developed below. They are designated under (Va) when the aromatic ring is 6 atoms and under (Vb) for a 5 atomic aromatic ring
    Figure imgb0005

Dans les formules générales ci-dessus, A représente un cation monovalent, X représente indépendamment un atome de carbone, un atome d'oxygène, un atome de soufre, un atome de phosphore ou un atome d'azote.In the general formulas above, A represents a monovalent cation, X independently represents a carbon atom, an oxygen atom, a sulfur atom, a phosphorus atom or a nitrogen atom.

Lorsque X représente un atome de carbone, de phosphore ou azote, les substituants peuvent être indépendamment des groupements electro-attracteurs ou électro-donneurs définis par un paramètre de Hammett (le paramètre de Hammett est une constante tabulée qui est déterminée pour une série de groupes substituants en mesurant la constante de dissociation des acides benzoïques correspondants) compris entre -0,7 et 1,0. De préférence, les substituants sont choisis parmi un groupement cyano (CN), un groupement R1, un groupement éther de type OR1, un groupement amino de type N(R1)2, un groupement ester de type CO2R1, un groupement sulfonyle type SO2R1 ou un groupement phosphonyle type PO2R1, où R1 a pour formule CnHmX'p avec n compris entre 0 et 6, m compris entre 0 et 13, X' est un halogéne (F, CI, Br et I) et p compris entre 1 et 13.When X represents a carbon, phosphorus or nitrogen atom, the substituents may be independently electron-withdrawing or electro-donor groups defined by a Hammett parameter (the Hammett parameter is a tabulated constant which is determined for a series of groups substituents by measuring the dissociation constant of the corresponding benzoic acids) between -0.7 and 1.0. Preferably, the substituents are chosen from a cyano group (CN), an R 1 group, an OR 1 type ether group, an N (R 1 ) 2 type amino group, and a CO 2 R 1 type ester group. a sulfonyl group type SO 2 R 1 or a phosphonyl group type PO 2 R 1 , where R 1 has the formula C n H m X ' p with n between 0 and 6, m between 0 and 13, X' is a halogen (F, Cl, Br and I) and p between 1 and 13.

L'invention concerne en premier lieu les composés imidazole bicycliques (IV) et leurs sels (V).The invention firstly relates to bicyclic imidazole compounds (IV) and their salts (V).

L'invention concerne en deuxième lieu les procédés de fabrication de composés imidazole bicycliques (IV) et leurs sels (V).The invention relates secondly to the processes for producing bicyclic imidazole compounds (IV) and their salts (V).

L'invention concerne en troisième lieu l'utilisation des composés de formule (V).Thirdly, the invention relates to the use of compounds of formula (V).

DESCRIPTION DETAILLEE DE L'INVENTIONDETAILED DESCRIPTION OF THE INVENTION

L'invention est maintenant décrite plus en détail et de façon non limitative dans la description qui suit.The invention is now described in more detail and without limitation in the description which follows.

Les sels des composés imidazole bicycliques (V), selon la présente invention sont représentés par la formule générale ci-dessus dans laquelle A représente un cation monovalent A, par exemple un métal alcalin.The salts of the bicyclic imidazole compounds (V) according to the present invention are represented by the above general formula wherein A represents a monovalent cation A, for example an alkali metal.

Le métal alcalin préféré est choisi parmi le lithium et le sodium.The preferred alkali metal is selected from lithium and sodium.

Lorsque X dans la formule générale représente un atome de carbone, de phosphore ou d'azote, les sels (V) peuvent être substitués. Les substituants préférés sont des groupements électro-attracteurs ou électro-donneurs, en particulier ceux ayant un paramètre de Hammett compris entre -0,7 et 1.When X in the general formula represents a carbon, phosphorus or nitrogen atom, the salts (V) may be substituted. The preferred substituents are electron-withdrawing or electro-donating groups, in particular those having a Hammett parameter between -0.7 and 1.

Les groupements électro-attracteurs et électro-donneurs particulièrement préférés, sont choisis parmi un groupement cyano (CN), un groupement R1, un groupement éther de type OR1, un groupement amino de type N(R1)2, un groupement ester de type CO2R1, un groupement sulfonyle type SO2R1 ou un groupement phosphonyle type PO2R1. où R1 a pour formule CnHmX'p avec n compris entre 0 et 6, m compris entre 0 et 13, X' est un halogéne (F, CI, Br et I) et p compris entre 1 et 13.Particularly preferred electro-attracting and electro-donating groups are chosen from a cyano group (CN), a group R 1 , an ether group of type OR 1 , an amino group of type N (R 1 ) 2 , an ester group of type CO 2 R 1 , a sulfonyl group type SO 2 R 1 or a phosphonyl group type PO 2 R 1 . where R 1 has the formula C n H m X ' p with n between 0 and 6, m between 0 and 13, X' is a halogen (F, Cl, Br and I) and p is between 1 and 13.

Préparation des sels des composés d'imidazole bicycliques (imidazolates bicycliques) et des composés d'imidazole bicycliquesPreparation of salts of bicyclic imidazole compounds (bicyclic imidazolates) and bicyclic imidazole compounds

Les imidazolates bicycliques (V) peuvent être préparés à partir des composés imidazole (IV) en faisant réagir celui-ci avec une base AZ, avec A ayant la même signification que ci-dessus et Z représentant un anion hydrure, hydroxyde ou carbonate. De préférence AZ est choisi parmi l'hydrure de lithium, le carbonate de lithium, l'hydroxyde de lithium, l'hydrure de sodium, le carbonate de sodium, l'hydroxyde de sodium et les combinaisons de ceux-ci.

        IV + AZ → V + AH

The bicyclic imidazolates (V) can be prepared from the imidazole compounds (IV) by reacting it with an AZ base, with A having the same meaning as above and Z representing a hydride, hydroxide or carbonate anion. Preferably AZ is selected from lithium hydride, lithium carbonate, lithium hydroxide, sodium hydride, sodium carbonate, sodium hydroxide and combinations thereof.

IV + AZ → V + AH

Les composés (IV) peuvent être préparés à partir de la condensation d'un aldéhyde aromatique de formule générale (II) et du DAMN (I).Compounds (IV) can be prepared from the condensation of an aromatic aldehyde of general formula (II) and DAMN (I).

Le procédé de préparation des composés imidazole bicycliques (IV) comprend (i) une étape réactionnelle du DAMN de formule (I) avec un aldéhyde aromatique de formule générale (II) à une température comprise entre 0 et 80°C, de préférence de 10 à 50°C, plus préférentiellement de 20 à 30°C, en présence éventuellement d'un solvant pour donner un composé de formule (III), suivie (ii) d'une étape de deshydrogénation du composé de formule (III).

        DAMN + II → III + H2O     (i)

        III - H2 → IV     (ii)

The process for the preparation of the bicyclic imidazole compounds (IV) comprises (i) a reaction step of the DAMN of formula (I) with an aromatic aldehyde of general formula (II) at a temperature of between 0 and 80 ° C, preferably at 50 ° C, more preferably from 20 to 30 ° C, optionally in the presence of a solvent to give a compound of formula (III), followed (ii) a dehydrogenation step of the compound of formula (III).

DAMN + II → III + H 2 O (i)

III - H 2 → IV (ii)

L'étape (i) est de préférence mise en oeuvre en présence d'un solvant. Tout composé permettant de solubiliser le(s) réactif(s) peut être utilisé comme solvant. A titre indicatif, on peut citer le dioxane, l'acétonitrile, ou l'ethanol.Step (i) is preferably carried out in the presence of a solvent. Any compound that solubilizes the reagent (s) can be used as a solvent. As an indication, mention may be made of dioxane, acetonitrile or ethanol.

Lorsque l'étape (i) est mise en oeuvre en présence d'un solvant, la concentration du DAMN dans le milieu réactionnel est de préférence de 0,001 à 2 mol/l, plus préférentiellement de 0,1 mol/l à 1 mol/l. Le rapport molaire du composé (I) sur le composé (II) est de préférence de 0,25 à 1,5, plus préférentiellement de 0,5 à 1,25.When step (i) is carried out in the presence of a solvent, the concentration of the DAMN in the reaction medium is preferably from 0.001 to 2 mol / l, more preferably from 0.1 mol / l to 1 mol / l. The molar ratio of the compound (I) to the compound (II) is preferably from 0.25 to 1.5, more preferably from 0.5 to 1.25.

La durée de l'étape (i) est de préférence de 1 à 12 heures, plus particulièrement de 1 à 5 heures, par exemple d'environ 2 heures.The duration of step (i) is preferably 1 to 12 hours, more preferably 1 to 5 hours, for example about 2 hours.

De préférence, l'étape (i) est mise en oeuvre en présence d'un catalyseur acide, éventuellement par ajout d'acide sulfurique ou d'un acide carboxylique, tel que l'acide trifluoroacétique, l'acide acétique ou l'acide benzoïque dans le milieu réactionnel.Preferably, step (i) is carried out in the presence of an acidic catalyst, optionally by adding sulfuric acid or a carboxylic acid, such as trifluoroacetic acid, acetic acid or acid. benzoic acid in the reaction medium.

Selon un mode de réalisation de l'invention, la température de la réaction peut être constante tout au long de la première étape.According to one embodiment of the invention, the temperature of the reaction can be constant throughout the first step.

Selon un autre mode de réalisation de l'invention, la température est croissante tout au long de l'étape (i).According to another embodiment of the invention, the temperature is increasing throughout step (i).

L'etape (ii) peut être réalisée en présence de composé suceptible de réagir avec l'hydrogène, comme l'oxygène, l'eau oxygénée et les péroxydes, le N-chlorosuccinimide, le N-bromosuccinimide, le chlorure d'hydroxyle, le fluorure d'hydroxyle , les composés à squelette type quinoneStep (ii) can be carried out in the presence of a compound capable of reacting with hydrogen, such as oxygen, hydrogen peroxide and peroxides, N-chlorosuccinimide, N-bromosuccinimide, hydroxyl chloride, hydroxyl fluoride, quinone-type skeleton compounds

A l'issue de cette réaction, le composé imidazole bicyclique de formule (IV) est de préférence isolé et purifié.At the end of this reaction, the bicyclic imidazole compound of formula (IV) is preferably isolated and purified.

Ainsi, le milieu réactionnel peut être évaporé et l'imidazole (III) recristallisé dans de l'eau pour ensuite être récupéré par filtration. Le solide obtenu peut être dissous dans une solution aqueuse de base AZ, de préférence lithiée ou sodée avec une concentration allant de 10-5 mol/l à la concentration de saturation. Une fois le sel de composé de formule (IV) est formé la solution peut subir plusieurs traitements au charbon actif. La solution peut ensuite être évaporée pour donner le sel de formule (IV).Thus, the reaction medium can be evaporated and the imidazole (III) recrystallized from water and then recovered by filtration. The solid obtained can be dissolved in an aqueous solution of AZ base, preferably lithiated or sodized with a concentration ranging from 10 -5 mol / l to the saturation concentration. Once the compound salt of formula (IV) is formed the solution can undergo several treatments with activated carbon. The solution can then be evaporated to give the salt of formula (IV).

PréparationPreparation d'un électrolytean electrolyte

Les composés de formule (V) peuvent être utilisés pour la préparation d'un électrolyte, en les dissolvant dans un solvant approprié.The compounds of formula (V) can be used for the preparation of an electrolyte, dissolving them in a suitable solvent.

Le solvant peut être constitué d'au moins un composé choisi parmi les carbonates, les glymes, les nitriles et les sulfones.The solvent may consist of at least one compound selected from carbonates, glymes, nitriles and sulfones.

Comme carbonate, on peut citer notamment l'éthylene carbonate, le dimethylcarbonate, l'éthylméthylcarbonate, le diéthylcarbonate, le propylene carbonate, carbonate de glycerol.As carbonate, there may be mentioned in particular ethylene carbonate, dimethylcarbonate, ethylmethylcarbonate, diethylcarbonate, propylene carbonate, glycerol carbonate.

Comme glymes on peut citer notamment l'éthylène glycol diméthyléther, le diéthylène glycol diméthyléther, le dipropylène glycol diméthyléther, le diéthylène glycol diéthyléther, le triéthylène glycol diméthyléther, le diéthylène glycol dibutyléther, le tétraéthylène glycol diméthyléther et le diéthylène glycol t-buthylméthyléther.As glymes mention may be made in particular of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether and diethylene glycol t-butyl methyl ether.

Comme nitriles on peut citer notamment, l'acétonitrile, le propionitrile, le butyronitrile, le méthoxypropionitrile, l'isobutyronitrile et les composés fluorés dérivants des composés précédents.Examples of nitrites that may be mentioned include acetonitrile, propionitrile, butyronitrile, methoxypropionitrile, isobutyronitrile and fluorinated compounds derived from the foregoing compounds.

Comme sulfones on peut notamment citer le diméthylsulfone, le sulfolane, l'éthylméthylsulfone, le propylméthylsulfone, l'isopropylméthylsulfone, l'isopropyléthylsulfone, le tertbutyléthylsulfone, le tertbutylméthylsulfone et le tertbutylpropylsulfone.Examples of sulfones that may be mentioned include dimethylsulfone, sulfolane, ethylmethylsulfone, propylmethylsulfone, isopropylmethylsulfone, isopropylethylsulfone, tertbutylethylsulfone, tertbutylmethylsulfone and tertbutylpropylsulfone.

Le solvant est de préférence constitué d'un mélange de composés, avantageusement de 2 à 5 choisis parmi les carbonates et/ou glymes et/ou les sulfones précédemment cités.The solvent is preferably composed of a mixture of compounds, advantageously from 2 to 5, chosen from the carbonates and / or glymes and / or the sulphones mentioned above.

Les proportions en poids de chacun des composés constituant le solvant sont de préférence comprises entre 1 et 10 par rapport au constituant en plus faible quantité, plus préférentiellement entre 1 et 8.The proportions by weight of each of the compounds constituting the solvent are preferably between 1 and 10 with respect to the constituent in a smaller amount, more preferably between 1 and 8.

La concentration en composé de formule (V) dans l'électrolyte est de préférence de 0,1 mol/l à 5 mol/l, plus préférentiellement de 0,2 mol/l à 2,5 mol/l. De préférence, l'électrolyte est constitué d'un mélange d'au moins deux sels de lithium choisi parmi le sel d'imidazolate (IV), le LiPF6, le LiBF4, le CF3COOLi, le CF3SO2Li, le LiTFSI (bis(trifluoromethanesulfonyl)imidure de lithium), le LiFSI (bis(fluorosulfonyl)imidure de lithium), le LiTDI (1-trifluorométhyl-4,5-dicarbonitrile-imidazolate de lithium) et le LiPDI (1-pentafluoroéthyl-4,5-dicarbonitrile-imidazolate de lithium). La quantité de chaque sel de lithium présent dans le mélange peut varier dans de larges limites et représente en général, entre 0,1 et 99,9 % en poids par rapport au poids total des sels présents dans le mélange, et de préférence entre 1 et 99 % en poids.The concentration of compound of formula (V) in the electrolyte is preferably from 0.1 mol / l to 5 mol / l, more preferably from 0.2 mol / l to 2.5 mol / l. Preferably, the electrolyte consists of a mixture of at least two lithium salts selected from the imidazolate salt (IV), LiPF 6 , LiBF 4 , CF 3 COOLi, CF 3 SO 2 Li LiTFSI (lithium bis (trifluoromethanesulfonyl) imide), LiFSI (lithium bis (fluorosulfonyl) imide), lithium LiTDI (lithium 1-trifluoromethyl-4,5-dicarbonitrile-imidazolate) and LiPDI (1-pentafluoroethyl). 4,5-dicarbonitrile-lithium imidazolate). The amount of each lithium salt present in the mixture can vary within wide limits and generally represents between 0.1 and 99.9% by weight relative to the total weight of the salts present in the mixture, and preferably between 1 and and 99% by weight.

EXEMPLEEXAMPLE

L'exemple suivant illustre l'invention sans la limiter.The following example illustrates the invention without limiting it.

On ajoute quelques gouttes d'acide sulfurique, dans 50 ml d'acétonitrile, contenant 1,19 g de DAMN préalablement dissous, et 1,47g de p-CN-benzaldéhyde .Un précipité jaune apparaît alors. La réaction est laissée sous agitation pendant 3 heures. La solution est filtrée et le solide est rincé avec de l'acétonitrile puis de l'éther. Le solide est ensuite séché sous vide à 110°C.A few drops of sulfuric acid are added in 50 ml of acetonitrile, containing 1.19 g of DMAM previously dissolved, and 1.47 g of p-CN-benzaldehyde. A yellow precipitate then appears. The reaction is stirred for 3 hours. The solution is filtered and the solid is rinsed with acetonitrile and then with ether. The solid is then dried under vacuum at 110 ° C.

Dans un ballon de 50 ml, 0,94 g de K2CO3 puis 0,90 g de N-chlorosuccinimide sont ajoutés à 1,0 g du solide précédemment obtenu dissous dans 25 mL de dimethylformamide. La solution est agitée à température ambiante pendant une nuit. 150 ml d'eau sont ajoutés en fin de réaction. La solution est acidifiée jusqu'à pH = 1 avec de l'acide sulfurique. La phase aqueuse est alors extraite avec 2 fois 100 mL d'acétate d'éthyle. Les phases organiques sont séchées puis évaporées. L'analyse RMN du résidu montre la présence du produit désiré. Le résidu est repris dans de l'eau en présence d'un excès de carbonate de lithium. La solution est agitée à température ambiante pendant 3 heures. La solution est filtrée puis extraite avec 2 fois 250 mL d'éther. La phase aqueuse est ensuite traitée au charbon actif pendant 2 heures à 50°C. La solution est filtrée puis évaporée. Le résidu est ensuite repris dans de l'acétonitrile, la partie insoluble correspondant au carbonate de lithium est éliminée par filtration. Le filtrat est alors évaporé et donne un solide jaune qui est le sel de lithium de formule suivante :

Figure imgb0006
In a 50 ml flask, 0.94 g of K 2 CO 3 and 0.90 g of N-chlorosuccinimide are added to 1.0 g of the previously obtained solid dissolved in 25 ml of dimethylformamide. The solution is stirred at room temperature overnight. 150 ml of water are added at the end of the reaction. The solution is acidified to pH = 1 with sulfuric acid. The aqueous phase is then extracted with 2 times 100 ml of ethyl acetate. The organic phases are dried and then evaporated. NMR analysis of the residue shows the presence of the desired product. The residue is taken up in water in the presence of an excess of lithium carbonate. The solution is stirred at ambient temperature for 3 hours. The solution is filtered and extracted with 2 times 250 ml of ether. The aqueous phase is then treated with activated carbon for 2 hours at 50 ° C. The solution is filtered and then evaporated. The residue is then taken up in acetonitrile, the insoluble part corresponding to the lithium carbonate is removed by filtration. The filtrate is then evaporated to give a yellow solid which is the lithium salt of the following formula:
Figure imgb0006

Le sel (V-1) est ensuite dissous à différentes concentrations dans un mélange d'éthylène carbone et de diméthylcarbonate avec un rapport massique de 1. La conductivité ionique des différentes concentrations est ensuite mesurée par spectroscopie d'impédance (figure 1). La stabilité électrochimique du sel (V-1) par rapport au Li+/Li est ensuite déterminée par voltamétrie cyclique d'une solution du sel (V-1) à 1 mol/L dans un mélange éthylène carbonate et diméthylcarbonate avec un rapport massique de 1 (figure 2).The salt (V-1) is then dissolved at different concentrations in a mixture of ethylene carbon and dimethyl carbonate with a mass ratio of 1. The ionic conductivity of the different concentrations is then measured by impedance spectroscopy (FIG. 1). The electrochemical stability of the salt (V-1) relative to Li + / Li is then determined by cyclic voltammetry of a solution of salt (V-1) at 1 mol / L in an ethylene carbonate and dimethyl carbonate mixture with a mass ratio of 1 ( figure 2 ).

Claims (13)

  1. A process for the preparation of a salt of the bicyclic imidazole compound (V) represented by the expanded general formulae below:
    Figure imgb0017
     in which A represents a monovalent cation and X independently represents a carbon atom, an oxygen atom, a sulfur atom, a phosphorus atom or a nitrogen atom, characterized in that an imidazole compound of formula (IV) represented by the expanded general formulae below:
    Figure imgb0018
     is reacted with a base AZ, with A having the same meaning as above and Z representing a hydride, hydroxide or carbonate anion.
  2. The process for the preparation of a salt as claimed in claim 1, characterized in that the monovalent cation A is an alkali metal, preferably chosen from lithium or sodium.
  3. The process for the preparation of a salt as claimed in claim 1 or 2, characterized in that X represents a carbon, phosphorus or nitrogen atom.
  4. The process for the preparation of a salt as claimed in claim 3, characterized in that said salt is substituted with an electron-withdrawing or an electron-donating group preferably chosen from a cyano (CN) group, an R1 group, an ether group of OR1 type, an amino group of N(R1)2 type, an ester group of CO2R1 type, a sulfonyl group of SO2R1 type or a phosphonyl group of PO2R1 type, where R1 has the formula CnHmX'p with n between 0 and 6, m between 0 and 13, X' a halogen (F, Cl, Br and I) and p between 1 and 13.
  5. The process for the preparation of a salt as claimed in claim 4, characterized in that the electron-withdrawing or electron-donating group is chosen from hydrogen, fluorine, the cyano (CN) group, the trifluoromethyl (CF3) group, the trifluoromethoxy (OCF3) group or the methoxy (OCH3) group.
  6. The process as claimed in any one of claims 1 to 5, characterized in that the base AZ is chosen from lithium hydride, lithium carbonate, lithium hydroxide, sodium hydride, sodium carbonate, sodium hydroxide and the combinations of these.
  7. The process as claimed in any one of claims 1 to 6, characterized in that the imidazole compounds (IV) are obtained by condensation of an aromatic aldehyde of general formula (II) represented by the expanded general formulae below:
    Figure imgb0019
     with DAMN (diaminomaleonitrile) represented by the formula (I) below:
    Figure imgb0020
     followed by dehydrogenation of the intermediate compound thus obtained of general formula (III) represented by the expanded general formulae below:
    Figure imgb0021
  8. The process as claimed in claim 7, comprising (i) a stage of reaction of DAMN of formula (I) with an aromatic aldehyde of several formula (II) at a temperature of between 0 and 80°C, preferably from 10 to 50°C, more preferably from 20 to 30°C, optionally in the presence of a solvent, to give a compound of formula (III), followed (ii) by a stage of dehydrogenation of said compound of formula (III).
  9. The process as claimed in claim 7 or claim 8, characterized in that stage (i) is carried out in the presence of a solvent.
  10. The process as claimed in claim 9, characterized in that the solvent is chosen from dioxane, acetonitrile or ethanol.
  11. The process as claimed in any one of claims 7 to 10, characterized in that stage (i) is carried out in the presence of an acid catalyst.
  12. The process as claimed in claim 11, characterized in that the acid catalyst is chosen from sulfuric acid, trifluoroacetic acid, acetic acid or benzoic acid.
  13. The process as claimed in any one of claims 7 to 12, characterized in that stage (ii) of dehydrogenation is carried out in the presence of an oxidizing agent, such as oxygen, hydrogen peroxide, peroxides, N-chlorosuccinimide, N-bromosuccinimide, hypochlorous acid, hypofluorous acid or compounds comprising a quinone-type backbone.
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